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Iron-Salen Complex and Co²⁺ Ion-Derived Cobalt-Iron Hydroxide/Carbon Nanohybrid as an Efficient Oxygen Evolution Electrocatalyst.

ABSTRACT: Metal-salen complexes are widely used as catalysts in numerous fundamental organic transformation reactions. Here, CoFe hydroxide/carbon nanohybrid is reported as an efficient oxygen evolution electrocatalyst derived from the in situ formed molecular Fe-salen complexes and Co²⁺ ions at a low temperature of 160 °C. It has been evidenced that Fe-salen as a molecular precursor facilitates the confined-growth of metal hydroxides, while Co²⁺ plays a critical role in catalyzing the transformation of organic ligand into nanocarbons and constitutes an essential component for CoFe hydroxide. The resulting Co_1.2Fe/C hybrid material requires an overpotential of 260 mV at a current density of 10 mA cm^-2 with high durability. The high activity is contributed to uniform distribution of CoFe hydroxides on carbon layer and excellent electron conductivity caused by intimate contact between metal and nanocarbon. Given the diversity of molecular precursors, these results represent a promising approach to high-performance carbon-based water splitting catalysts.

SUBMITTER: Du J

PROVIDER: S-EPMC6662268 | biostudies-literature | 2019 Jun

REPOSITORIES: biostudies-literature

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Iron-Salen Complex and Co2+ Ion-Derived Cobalt-Iron Hydroxide/Carbon Nanohybrid as an Efficient Oxygen Evolution Electrocatalyst.

Du Jian J Liu Guoquan G Li Fei F Zhu Yong Y Sun Licheng L

Advanced science (Weinheim, Baden-Wurttemberg, Germany) 20190415 12

Metal-salen complexes are widely used as catalysts in numerous fundamental organic transformation reactions. Here, CoFe hydroxide/carbon nanohybrid is reported as an efficient oxygen evolution electrocatalyst derived from the in situ formed molecular Fe-salen complexes and Co2+ ions at a low temperature of 160 °C. It has been evidenced that Fe-salen as a molecular precursor facilitates the confined-growth of metal hydroxides, while Co2+ plays a critical role in catalyzing t ...[more]

PMID: 31380163

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Project description:The quest for developing next-generation non-precious electrocatalysts has risen in recent times. Herein, we have designed and developed a low cost electrocatalyst by a ligand-assisted synthetic strategy in an aqueous medium. An oxalate ligand-assisted non-oxide electrocatalyst was developed by a simple wet-chemical technique for alkaline water oxidation application. The synthetic parameters for the preparation of nickel-cobalt oxalate (Ni2.5Co5C2O4) were optimized, such as the metal precursor (Ni/Co) ratio, oxalic acid amount, reaction temperature, and time. Microstructural analysis revealed a mesoporous block-like architecture for nickel-cobalt oxalate (Ni2.5Co5C2O4). The required overpotential of Ni2.5Co5C2O4 for the alkaline oxygen evolution reaction (OER) was found to be 330 mV for achieving 10 mA cmgeo -2, which is superior to that of NiC2O4, CoC2O4, NiCo2O4 and the state-of-the-art RuO2. The splendid performance of Ni2.5Co5C2O4 was further verified by its low charge transfer resistance, impressive stability performance, and 87% faradaic efficiency in alkaline medium (pH = 14). The improved electrochemical activity was further attributed to double layer capacitance (C dl), which indefinitely divulged the inferiority of NiCo2O4 compared to Ni2.5Co5C2O4 for the alkaline oxygen evolution reaction (OER). The obtained proton reaction order (ρ RHE) was about 0.80, thus indicating the proton decoupled electron transfer (PDET) mechanism for OER in alkaline medium. Post-catalytic investigation revealed the formation of a flake-like porous nanostructure, indicating distinct transformation in morphology during the alkaline OER process. Further, XPS analysis demonstrated complete oxidation of Ni2+ and Co2+ centres into Ni3+ and Co3+, respectively under high oxidation potential, thereby indicating active site formation throughout the microstructural network. Additionally, from BET-normalised LSV investigation, the intrinsic activity of Ni2.5Co5C2O4 was also found to be higher than that of NiCo2O4. Finally, Ni2.5Co5C2O4 delivered a TOF value of around 3.28 × 10-3 s-1, which is 5.56 fold that of NiCo2O4 for the alkaline OER process. This report highlights the unique benefit of Ni2.5Co5C2O4 over NiCo2O4 for the alkaline OER. The structure-catalytic property relationship was further elucidated using density functional theory (DFT) study. To the best of our knowledge, nickel-cobalt oxalate (Ni2.5Co5C2O4) was introduced for the first time as a non-precious non-oxide electrocatalyst for alkaline OER application.

Dataset Information

Iron-Salen Complex and Co²⁺ Ion-Derived Cobalt-Iron Hydroxide/Carbon Nanohybrid as an Efficient Oxygen Evolution Electrocatalyst.

Publications

Iron-Salen Complex and Co<sup>2+</sup> Ion-Derived Cobalt-Iron Hydroxide/Carbon Nanohybrid as an Efficient Oxygen Evolution Electrocatalyst.

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